Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 33, Pages 13804-13817Publisher
AMER CHEMICAL SOC
DOI: 10.1021/Ja305441d
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Funding
- American Chemical Society Petroleum Research Fund
- National Institutes of Health Doctoral Studies in Molecular Biophysics Training [5 T32GM008271]
- NSF [CNS-0619508]
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The influence of alkene functionality on the energetics and kinetics of radical initiated thiol-ene click chemistry has been studied computationally at the CBS-QB3 level. Relative energetics (Delta H degrees, Delta H-double dagger, Delta G degrees, Delta G(double dagger)) have been determined for all stationary points along the step-growth mechanism of thiol-ene reactions between methyl mercaptan and a series of 12 alkenes: propene, methyl vinyl ether, methyl allyl ether, norbornene, acrylonitrile, methyl acrylate, butadiene, methyl(vinyl)silanediamine, methyl crotonate, dimethyl fumarate, styrene, and maleimide. Electronic structure calculations reveal the underlying factors that control activation barriers for propagation and chain-transfer processes of the. step-growth mechanism. Results are further extended to predict rate constants for forward and reverse propagation and chain-transfer steps (k(P), k(-P), k(CT), k(-CT)) and used to model overall reaction kinetics. A relationship between alkene structure and reactivity in thiol-ene reactions is derived from the results of kinetic modeling and can be directly related to the relative energetics of stationary points obtained from electronic structure calculations. The results predict the order of reactivity of alkenes and have broad implications for the use and applications of thiol-ene click chemistry.
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